Hard surface cleaner comprising a suspension of alginate beads

ABSTRACT

The present invention is directed to a pourable acidic hard surface cleaning and/or disinfecting composition which contains suspended inclusions which appear as visibly discernible, discrete particulate materials, preferably where said discrete particulate materials are based on alginates.

The present application is a continuation in part application filedunder 35 USC 111(a) of International Applications PCT/GB02/03407 filedJul. 25, 2002 and PCT/GB04/000589 filed Feb. 17, 2004.

The present invention relates to pourable disinfecting hard surfacecleaning compositions. More particularly the present invention relatesto thickened lavatory cleaning compositions which provide a cleaning anddisinfecting effect to hard surfaces, and which include visiblydiscernible inclusions.

Cleaning compositions which also provide a disinfecting or sanitizingeffect are commercially important products. Such compositions enjoy awide field of utility in assisting in the removal of stains and grimefrom surfaces, especially those characterized as useful with “hardsurfaces”. Hard surfaces are those which are frequently encountered inlavatories such as lavatory fixtures such as toilets, shower stalls,bathtubs, bidets, sinks, etc., as well as countertops, walls, floors,etc. Two types of commonly encountered stains in lavatories include“hard water” stains and “soap scum” stains. Such hard surfaces, and suchstains, may also be found in different environments as well, includingkitchens, hospitals, etc.

Various formulations in compositions of cleaning agents have beenproduced and are known to the art which cleaning agents are generallysuited for one type of stain but not necessarily for both classes ofstains. For example, it is known to the art that highly acidic cleaningagents comprising strong acids, such as hydrochloric acids, are usefulin the removal of hard water stains. However, the presence of strongacids is known to be an irritant to the skin and further offers thepotential of toxicological danger. Other classes of cleaningcompositions and formulations are known to be useful upon soap scumstains, however, generally such compositions comprise an organic and/orinorganic acid, one or more synthetic detergents from commonlyrecognized classes such as those described in U.S. Pat. No. 5,061,393;U.S. Pat. No. 5,008,030; U.S. Pat. No. 4,759,867; U.S. Pat. No.5,192,460; U.S. Pat. No. 5,039,441. Generally, the compositionsdescribed in these patents are claimed to be effective in the removal ofsoap scum stains from such hard surfaces and may find further limiteduse in other classes of stains.

However, the formulations of most of the compositions within theaforementioned patents generally have relatively high amounts of acids(organic and/or inorganic) which raises toxicological concerns, andfurther none of the above patents provide any disinfecting properties.

While many disinfecting hard surface cleaning compositions are known tothe art, there is nonetheless a need for further improved compositionsin the art.

According to the one aspect of the invention, there is provided a liquidpourable hard surface cleaning and/or disinfecting composition whichcomprises (preferably consists essentially of):

an acid constituent;

at least one nonionic surfactant;

suspended inclusions which appear as visibly discernible, discreteparticulate materials, preferably where said discrete particulatematerials are based on alginates; a thickener constituent;

optionally, at least one further detersive surfactant selected fromanionic, amphoteric and zwitterionic surfactants;

optionally, but desirably at least one organic solvent;

optionally, one or more constituents for improving the aesthetic orfunctional features of the inventive compositions; and;

water.

Particularly preferred compositions according to the invention areacidic in character, are effective in the removal of both soap scumstains and hard water stains, and which compositions provide aneffective sanitizing effect to hard surfaces.

In further aspects of the invention there are provided processes for theproduction of the aforesaid compositions.

It is yet a further object of the invention to provide a liquid pourablecleaning composition which features the benefits described above.

It is a further object of the invention to provide a process for thesimultaneous cleaning and sanitization of hard surfaces, which processcomprises the step of providing a composition as outlined above, andapplying an effective amount to a hard surface requiring such treatment.

The present inventive compositions necessarily comprise an acidconstituent which be a water soluble inorganic acid, or a water solubleorganic acids. By way of non-limiting example useful inorganic acidsinclude hydrochloric acid, phosphoric acid, sulfuric acid acid. Withrespect to water soluble organic acids, generally include at least onecarbon atom, and include at least one carboxyl group (—COOH) in itsstructure. Preferred are water soluble organic acids which contain from1 to about 6 carbon atoms, and at least one carboxyl group as noted.Particularly preferred amongst such organic acids are: formic acid,citric acid, sorbic acid, acetic acid, boric acid, maleic acid, adipicacid, lactic acid, malic acid, malonic acid, glycolic acid, and mixturesthereof. According to certain preferred embodiments however, the acidconstituent is a combination of citric acid in combination with at leastone further acid selected from the group consisting of sorbic acid,acetic acid, boric acid, formic acid, maleic acid, adipic acid, lacticacid, formic acid, malic acid, malonic acid, and glycolic acid. Mostpreferably, the acid constituent is a combination of citric acid withlactic acid, glycolic acid or malic acid.

As the inventive compositions are necessarily acidic in nature (pH<7.0)there should be sufficient acid present in the composition such that thepH of the composition is desirably less than 6, preferably from about5.0 to about 1.0, more preferably from about 4.0 to about 1.0, and evenmore preferably from about 3.0 to about 1.0. Of course mixtures of twoor more acids may be used, and the acid constituent may be present inany effective amount to provide a desired pH. Desirably however, theacid constituents is present in an amount not in excess of 20% wt. basedon the total weight of the compositions; preferably the acid constituentis present in an amount of from about 0.05–20% wt., more preferably fromabout 0.5–20% wt., and most preferably is present in an amount of fromabout 1% wt. to about 15% wt.

The acid constituent of the inventive formulations provide free aciditywithin the cleaning composition, which free acid reacts with the fattyacid metal salts which are comprised within soap scum stains releasingthe metal ions and freeing the fatty acid, which facilitates the removalof these undesired stains from hard surfaces. These acids also sequesterthe resulting free metal ions which are released from the soap scumstains. Also where the acids are selected to feature disinfectingproperties, they concomitantly provide antimicrobial activity necessaryto disinfect the cleaned surface.

The compositions of the present invention necessarily includes at leastone anionic surfactant. Generally any anionic surfactant material may beused in the inventive compositions as this necessary constituent. By wayof non-limiting example, particularly suitable anionic surfactantsinclude: alkali metal salts, ammonium salts, amine salts, oraminoalcohol salts of one or more of the following compounds (linear andsecondary): alcohol sulfates and sulfonates, alcohol phosphates andphosphonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of analkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates,alkyl sulfonates, olefin sulfonates, paraffin sulfonates, beta-alkoxyalkane sulfonates, alkylamidoether sulfates, alkylaryl polyethersulfates, monoglyceride sulfates, alkyl ether sulfonates, ethoxylatedalkyl sulfonates, alkylaryl sulfonates, alkyl benzene sulfonates,alkylamide sulfonates, alkyl monoglyceride sulfonates; alkylcarboxylates, alkyl sulfoacetates, alkyl ether carboxylates, alkylalkoxy carboxylates having 1 to 5 moles of ethylene oxide, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, alkyl sulfosuccinamates, octoxynol or nonoxynolphosphates, alkyl phosphates, alkyl ether phosphates, taurates, N-acyltaurates, fatty taurides, fatty acid amide polyoxyethylene sulfates,isethionates, acyl isethionates, and sarcosinates, acyl sarcosinates, ormixtures thereof Generally, the alkyl or acyl radical in these variouscompounds comprise a carbon chain containing 12 to 20 carbon atoms.

Preferred anionic surfactants useful in forming the compositions of theinvention include alkyl sulfates which may be represented by thefollowing general formula:

wherein R is an straight chain or branched alkyl chain having from about8 to about 18 carbon atoms, saturated or unsaturated, and the longestlinear portion of the alkyl chain is 15 carbon atoms or less on theaverage, M is a cation which makes the compound water soluble especiallyan alkali metal such as sodium, or is ammonium or substituted ammoniumcation, and x is from 0 to about 4. Of these, most preferred are thenon-ethoxylated C₁₂–C₁₅ primary and secondary alkyl sulfates.

Exemplary commercially available alkyl sulfates include one or more ofthose available under the tradenames RHODAPON® (ex. Rhône-Poulenc Co.)as well as STEPANOL® (ex. Stepan Chemical Co.). Exemplary alkyl sulfateswhich is preferred for use is a sodium lauryl sulfate surfactantpresently commercially available as RHODAPON® LCP (ex. Rhône-PoulencCo.), as well as a further sodium lauryl sulfate surfactant compositionwhich is presently commercially available as STEPANOL® WAC (ex. StepanChemical Co.).

Further preferred anionic surfactants useful in forming the compositionsof the invention include alkyl sulfonate anionic surfactants which maybe represented according to the following general formula:

wherein R is an straight chain or branched alkyl chain having from about8 to about 18 carbon atoms, saturated or unsaturated, and the longestlinear portion of the alkyl chain is 15 carbon atoms or less on theaverage, M is a cation which makes the compound water soluble especiallyan alkali metal such as sodium, or is ammonium or substituted ammoniumcation, and x is from 0 to about 4. Most preferred are the C₁₂–C₁₅primary and secondary alkyl sulfates.

Exemplary, commercially available alkane sulfonate surfactants includeone or more of those available under the tradename HOSTAPUR® (ex.Clariant). An exemplary and particularly alkane sulfonate which ispreferred for use is a secondary sodium alkane sulfonate surfactantpresently commercially available as HOSTAPUR® SAS from Hoechst Celanese.

The anionic surfactant is present in the compositions of the presentinvention in an amount of from about 0.01 to about 20% by weight, morepreferably is present in an amount of from about 0.1–20% wt., and mostpreferably is present in an amount of from about 1% wt. to about 20% wt.

As a further necessary constituent, the inventive compositions comprisea thickener constituent. Thickeners useful in the present invention toachieve this viscosity are selected from the group consisting ofcellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkylcelluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses,carboxy alkyl hydroxy alkyl celluloses, xanthan gum, gellan gum andmixtures thereof. Examples of the cellulose derivatives include ethylcellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose, carboxymethyl cellulose, carboxy methyl hydroxyethyl cellulose, hydroxypropylcellulose, hydroxy propyl methyl cellulose, and ethyl hydroxy ethylcellulose. Preferably, the thickener is a mixture of hydroxy ethylcellulose and xanthan gum or is a mixture of xantham gum and gellan gum.Further specific preferred thickeners and combinations of thickeners aredescribed in the Examples.

The amount of thickener present in the composition may be any amountwhich is effective in suspending the suspended inclusions as hereinafterdescribed. Desirably the composition of the present of invention isthickened to a viscosity range of from about 100 to about 2000centipoise, preferably to a viscosity of from about 750 to about 1500centipoise, more preferably is in the range of about 800–1200 centipoisemeasured at room temperature, on a RVT Brookfield viscometer, spindle#2, at 60 rpm. Generally good thickening has been observed when thetotal amount of the thickeners are present in amount from about 0.1 toabout 5% by weight, more preferably from about 0.1 to about 4% byweight, and most preferably from about 0.1% wt. to about 1% wt.

Preferably other thickening materials, particularly those based onsynthetic polymers such as acrylic acid copolymers, e.g. Carbopol®materials, as well as those based on clays, and those based on celluloseincluding modified celluloses are desirably absent from the inventivecompositions.

As a necessary constituent, the inventive compositions include suspendedinclusions. These suspend inclusions appear as visibly discernible,discrete particulate materials to the consumer of the inventivecompositions. These suspended inclusions desirably appear as smalldiscrete visible particles suspended within the composition,particularly by a consumer having normal “20/20” vision. It is to beunderstood however that not all of the particulate materials present inthe inventive composition need be visibly discernible as a portion ofthe particulate materials may be smaller than the visible threshold ofthe consumer having normal vision. It is nonetheless required that atleast a substantial portion of the particulate materials present in theinventive composition need be visibly discernible as discrete particles.

Desirably the particulate materials are supplied to have an averageparticle size in the range of about 50 μm to about 1000 μm, preferablyin the range of about 350 μm to about 1000 μm, most preferably in therange of about 450 μm to about 650 μm, and especially preferably in therange of about 575 μm to about 625 μm. Desirably the average particlesize of these particulate materials represents that at least 85% of theparticles, more preferably at least 90%, still more preferably at least92%, and most preferably at least 90% of the particles present arewithin a specified range.

The suspended inclusions present in the inventive compositions are mostdesirably based on alginates although other visibly discernible,discrete particulate materials may be used as well, or in the place ofalginate based materials. However the particularly preferred suspendedinclusions are based on alginates.

Alginate based particulate materials used for the suspended inclusionsin the inventive compositions may be formed from an alginate or salts ofalginic acid such as potassium alginate, calcium alginate or sodiumalginate salts, and advantageously may be conveniently harvested fromnaturally occurring seaweed especially of the species Laminaria whereinthe sodium alginate form predominates. Alginates typically consist ofsequences of α-L-guluronic acid and β-D-mannuronic acid which may bepresent in the alginate in various differing ratios. The term “beads”conveniently describes the geometry of the alginate based particulatematerials as when these are formed form an aqueous slurry containing analginate such as sodium alginate with one or more further constituentsand then expelled to form individual particles or droplets, thecoalescing aqueous slurry may form generally spherical particles, hencethe term “beads”. Of course, other processes for the formation ofalginate based suspended inclusions are also contemplated as beinguseful in conjunction with the present invention such as processeswherein the alginate optionally containing one or more furtherconstituents is comminuted by other methods, such as milling, grindingor other known art technique. In such instances the comminuted alginatebased suspended inclusions may not necessarily form generally sphericalparticles but may form individual particles of irregular geometry. Insuch an instance the largest dimension of such individual particles ofirregular geometry are used as the basis for determining the averageparticle size of the In a preferred embodiment the alginate beads arebased on calcium alginates as the calcium salts of alginates areinsoluble or poorly soluble in water, and thus are particularlydesirable in the present inventive compositions which are substantiallyaqueous. The calcium salts of alginates used to form the alginate basedparticulate materials preferably exhibit little swelling or collapsewhen incorporated in the present inventive composition.

The alginate based particulate materials may contain from about 0.5% wt.to 100% wt. of an alginate or alginate salt, although quite frequentlythe amount of alginate in the alginate based particulate materials aremuch less, generally on from about 0.5% wt. to about 10% wt., morepreferably from about 0.5% wt. to about 5% wt. Such alginate basedparticulate materials may be conveniently referred to as “alginatebeads”. Such alginate beads may be formed by a variety of known artprocesses including those described in the background section ofPCT/US95/08313 to Thomas et al., as well as in U.S. Pat. No. 6,467,699B1, the contents of which are incorporated by reference. Alternatelysuch alginate based particulate materials may be commercially purchasedfrom various suppliers, including geniaLab BioTechnologie (Braunschwig,Germany). As noted the composition of the alginate based particulatematerials may include only a small proportion of an alginate or alginatesalt, and may include one or more further non-alginate materialsespecially one or more inorganic materials such as titanium dioxidewhich improves the opacity, hence the visibility of the beads, as wellas one or more coloring agents such as pigments such as ultramarineblue, said coloring agents which also improve the aesthetic appearanceof the beads. Other further non-alginate materials not recited hereinmay also be include in the composition of the alginate based particulatematerials. The alginate based particulate materials may be composed of amajor proportion of water which is entrained within the structure of thediscrete alginate based particulates and due to the highly porouscharacter of alginates when in an aqueous compositions 80% wt., andusually 90% wt. or even greater of the mass of the discrete alginatebased particulates may be water with the remaining balance to 100% wt.being the alginate or alginate salt, and one or more furthernon-alginate materials. Conveniently such alginate based particulatematerials may be prepared, stored and sold as a slurry of discretealginate based particulates in an aqueous-based carrier compositionwhich may contain a minor amount of one or more further additives suchas one or more salts especially chloride salts such as calcium chloride,as well as a preservative for inhibiting the growth of undesirablemicroorganisms in the slurry containing the discrete alginate basedparticulates. Preferred commercially available alginate basedparticulate material comprise from about 0.5% wt. to about 5% wt. of acalcium alginate, a pigment present in an amount up to about 0.01% wt.,from about 0.1% wt. to about 5% wt. of TiO2 and the remaining balance ofthe mass of the alginate based particulate material comprised of a 2%calcium chloride solution in water which may also con an a minor amount,approx. 2% of calcium chloride. Such alginate based particulate materialcan be separated from the aqueous-based carrier composition by means ofa fine sieve or other means for decanting the aqueous-based carriercomposition from the alginate based particulate materials.

By the term “suspended” when referring to the inclusions, is to beunderstood that when the formed inventive compositions are manuallyshaken and then allowed to return to a quiescent state, such as bypermitting them to stand on a tabletop or other surface at roomtemperature (approx. 20° C.) for 48 hours, the majority of theinclusions do not drop more than 7%, preferably do not drop more than5%, most preferably do not drop more than 2% of their original distanceas measured from the bottom of the container in which the inventivecomposition is present when they have returned to a quiescent statefollowing manual shaking. By “majority of inclusions” is meant to conveythat at least 90% of, preferably at least 95% and most preferably atleast 97% of the inclusions physically present in the compositions. Thisis a particularly attractive and characteristic feature of preferredembodiments of inventive compositions, as the suspended inclusions donot appear to move perceptibly over long periods of time. Desirably, atleast 90% of, preferably at least 95% and most preferably at least 97%of the inclusions physically present in the compositions do not dropmore than 5%, most preferably do not drop more than 2% of their originaldistance from the bottom of the container in which the inventivecomposition is present when they have returned to a quiescent statefollowing manual shaking when measured after 72 hours, more preferablywhen measured after 5 days, still more preferably when measured after 10days, yet more preferably after 14 days when left in a quiescent stateat room temperature. In certain particularly preferred embodiments ofthe invention at least 90% of, preferably at least 95% and mostpreferably at least 97% of the inclusions physically present in thecompositions do not drop more than 5%, after 3 weeks and especiallypreferably after 4 weeks when retained in a quiescent state at roomtemperature.

Although optional, the compositions according to the present inventionmay include one or more further detersive surfactants particularly thoseselected from amongst further nonionic, amphoteric and zwitterionicsurfactants, particularly those which may provide a detersive effect tothe compositions.

Generally any nonionic surfactant material may be used in the inventivecompositions. Practically any hydrophobic compound having a carboxy,hydroxy, amido, or amino group with a free hydrogen attached to thenitrogen can be condensed with an alkylene oxide, especially ethyleneoxide or with the polyhydration product thereof, a polyalkylene glycol,especially polyethylene glycol, to form a water soluble or waterdispersible nonionic surfactant compound. By way of non-limitingexample, particularly examples of suitable nonionic surfactants whichmay be used in the present invention include the following:

One class of useful nonionic surfactants include polyalkylene oxidecondensates of alkyl phenols. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to 12 carbon atoms in either a straight chain or branched chainconfiguration with an alkylene oxide, especially an ethylene oxide, theethylene oxide being present in an amount equal to 5 to 25 moles ofethylene oxide per mole of alkyl phenol. The alkyl substituent in suchcompounds can be derived, for example, from polymerized propylene,diisobutylene and the like. Examples of compounds of this type includenonyl phenol condensed with about 9.5 moles of ethylene oxide per moleof nonyl phenol; dodecylphenol condensed with about 12 moles of ethyleneoxide per mole of phenol; dinonyl phenol condensed with about 15 molesof ethylene oxide per mole of phenol and diisooctyl phenol condensedwith about 15 moles of ethylene oxide per mole of phenol.

A further class of useful nonionic surfactants include the condensationproducts of aliphatic alcohols with from about 1 to about 60 moles of analkylene oxide, especially an ethylene oxide. The alkyl chain of thealiphatic alcohol can either be straight or branched, primary orsecondary, and generally contains from about 8 to about 22 carbon atoms.Examples of such ethoxylated alcohols include the condensation productof myristyl alcohol condensed with about 10 moles of ethylene oxide permole of alcohol and the condensation product of about 9 moles ofethylene oxide with coconut alcohol (a mixture of fatty alcohols withalkyl chains varying in length from about 10 to 14 carbon atoms). Otherexamples are those C₆–C₁₁ straight-chain alcohols which are ethoxylatedwith from about 3 to about 6 moles of ethylene oxide. Their derivationis well known in the art. Examples include Alfonic® 810-4.5, which isdescribed in product literature from Sasol as a C8–10 having an averagemolecular weight of 356, an ethylene oxide content of about 4.85 moles(about 60 wt. %), and an HLB of about 12; Alfonic® 810-2, which isdescribed in product literature as a C₈–C₁₀ having an average molecularweight of 242, an ethylene oxide content of about 2.1 moles (about 40wt. %), and an HLB of about 12; and Alfonic® 610-3.5, which is describedin product literature as having an average molecular weight of 276, anethylene oxide content of about 3.1 moles (about 50 wt. %), and an HLBof 10. Other examples of alcohol ethoxylates are C10 oxo-alcoholethoxylates available from BASF under the Lutensol® ON tradename. Theyare available in grades containing from about 3 to about 11 moles ofethylene oxide (available under the names Lutensol® ON 30; Lutensol® ON50; Lutensol® ON 60; Lutensol® ON 65; Lutensol® ON 66; Lutensol® ON 70;Lutensol® ON 80; and Lutensol® ON 110). Other examples of ethoxylatedalcohols include the Neodol® 91 series non-ionic surfactants availablefrom Shell Chemical Company which are described as C₉–C₁₁ ethoxylatedalcohols. The Neodol® 91 series non-ionic surfactants of interestinclude Neodol® 91-2.5, Neodol® 91-6, and Neodol® 91-8. Neodol® 91-2.5has been described as having about 2.5 ethoxy groups per molecule,Neodol 91-6 has been described as having about 6 ethoxy groups permolecule; and Neodol 91-8 has been described as having about 8 ethoxygroups per molecule. Further examples of ethoxylated alcohols includethe Rhodasurf® DA series non-ionic surfactants available from Rhodiawhich are described to be branched isodecyl alcohol ethoxylates.Rhodasurf® DA-530 has been described as having 4 moles of ethoxylationand an HLB of 10.5; Rhodasurf® DA-630 has been described as having 6moles of ethoxylation with an HLB of 12.5; and Rhodasurf® DA-639 is a90% solution of DA-630. Further examples of ethoxylated alcohols includethose from Tomah Products (Milton, Wis.) under the Tomadol® tradenamewith the formula RO(CH₂CH₂O)_(n)H where R is the primary linear alcoholand n is the total number of moles of ethylene oxide. The ethoxylatedalcohol series from Tomah include 91-2.5; 91-6; 91-8—where R is linearC₉/C₁₀/C₁₁ and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R islinear C₁₁ and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5—where R islinear C₁₂/C₁₃ and n is 1, 3, 5, or 6.5; 25-3; 25-7, 25-9; 25-12—where Ris linear C₁₂/C₁₃/C₁₄/C₁₅ and n is 3, 7, 9, or 12; and 45-7; 45-13—whereR is linear C₁₄/C₁₅ and n is 7 or 13.

A further class of useful nonionic surfactants include primary andsecondary linear and branched alcohol ethoxylates, such as those basedon C₆–C₁₈ alcohols which further include an average of from 2 to 80moles of ethoxylation per mol of alcohol. These examples include theGenapol® UD (ex. Clariant, Muttenz, Switzerland) described under thetradenames Genapol® UD 030, C₁₁-oxo-alcohol polyglycol ether with 3 EO;Genapol® UD, 050 C₁₁-oxo-alcohol polyglycol ether with 5 EO; Genapol® UD070, C₁₁-oxo-alcohol polyglycol ether with 7 EO; Genapol® UD 080,C₁₁-oxo-alcohol polyglycol ether with 8 EO; Genapol® UD 088,C₁₁-oxo-alcohol polyglycol ether with 8 EO; and Genapol® UD 110,C₁₁-oxo-alcohol polyglycol ether with 11 EO.

A further class of useful nonionic surfactants includethose surfactantshaving a formula RO(CH₂CH₂O)_(n)H wherein R is a mixture of linear, evencarbon-number hydrocarbon chains ranging from C₁₂H₂₅ to C₁₆H₃₃ and nrepresents the number of repeating units and is a number of from about 1to about 12. Surfactants of this formula are presently marketed underthe Genapol® tradename (ex. Clariant), which surfactants include the“26-L” series of the general formula RO(CH₂CH₂O)_(n)H wherein R is amixture of linear, even carbon-number hydrocarbon chains ranging fromC₁₂H₂₅ to C₁₆H₃₃ and n represents the number of repeating units and is anumber of from 1 to about 12, such as 26-L-1, 26-L-1.6, 26-L-2, 26-L-3,26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L-60N, 26-L-75, 26-L-80, 26-L-98N,and the 24-L series, derived from synthetic sources and typicallycontain about 55% C₁₂ and 45% C₁₄ alcohols, such as 24-L-3, 24-L-45,24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N, all soldunder the Genapol® tradename.

A further class of useful nonionic surfactants include alkoxy blockcopolymers, and in particular, compounds based on ethoxy/propoxy blockcopolymers. Polymeric alkylene oxide block copolymers include nonionicsurfactants in which the major portion of the molecule is made up ofblock polymeric C₂–C₄ alkylene oxides. Such nonionic surfactants, whilepreferably built up from an alkylene oxide chain starting group, and canhave as a starting nucleus almost any active hydrogen containing groupincluding, without limitation, amides, phenols, thiols and secondaryalcohols.

One group of such useful nonionic surfactants containing thecharacteristic alkylene oxide blocks are those which may be generallyrepresented by the formula (A):HO—(EO)_(x)(PO)_(y)(EO)_(z)—H  (A)where

-   -   EO represents ethylene oxide,    -   PO represents propylene oxide,    -   y equals at least 15,    -   (EO)_(x+y) equals 20 to 50% of the total weight of said        compounds, and, the total molecular weight is preferably in the        range of about 2000 to 15,000. These surfactants are available        under the PLURONIC (ex. BASF) or Emulgen (ex. Kao.) A further        group of such useful nonionic surfactants containing the        characteristic alkylene oxide blocks are those can be        represented by the formula (B):        R—(EO,PO)_(a)(EO,PO)_(b)—H  (B)        wherein R is an alkyl, aryl or aralkyl group, where the R group        contains 1 to 20 carbon atoms, the weight percent of EO is        within the range of 0 to 45% in one of the blocks a, b, and        within the range of 60 to 100% in the other of the blocks a, b,        and the total number of moles of combined EO and PO is in the        range of 6 to 125 moles, with 1 to 50 moles in the PO rich block        and 5 to 100 moles in the EO rich block. Specific nonionic        surfactants which in general are encompassed by Formula B        include butoxy derivatives of propylene oxide/ethylene oxide        block polymers having molecular weights within the range of        about 2000–5000.

Still further examples of useful nonionic surfactants include thosewhich can be represented by formula (C) as follows:RO—(BO)_(n)(EO)_(x)—H  (C)wherein

-   -   EO represents ethylene oxide,    -   BO represents butylene oxide,

R is an alkyl group containing 1 to 20 carbon atoms,

-   -   n is about 5–15 and x is about 5–15.        Yet further useful nonionic surfactants include those which may        be represented by the following formula (D):        HO—(EO)_(x)(BO)_(n)(EO)_(y)—H  (D)        wherein    -   EO represents ethylene oxide,    -   BO represents butylene oxide,

n is about 5–15, preferably about 15,

-   -   x is about 5–15, preferably about 15, and    -   y is about 5–15, preferably about 15.        Still further exemplary useful nonionic block copolymer        surfactants include ethoxylated derivatives of propoxylated        ethylene diamine, which may be represented by the following        formula:

where

-   -   (EO) represents ethoxy,    -   (PO) represents propoxy,        the amount of (PO)_(x) is such as to provide a molecular weight        prior to ethoxylation of about 300 to 7500, and the amount of        (EO)_(y) is such as to provide about 20% to 90% of the total        weight of said compound.

Further useful non-ionic surfactants which may be used in the inventivecompositions include those presently marketed under the trade namePluronics® (ex. BASF). The compounds are formed by condensing ethyleneoxide with a hydrophobic base formed by the condensation of propyleneoxide with propylene glycol. The molecular weight of the hydrophobicportion of the molecule is of the order of 950 to 4,000 and preferably200 to 2,500. The addition of polyoxyethylene radicals of thehydrophobic portion tends to increase the solubility of the molecule asa whole so as to make the surfactant water-soluble. The molecular weightof the block polymers varies from 1,000 to 15,000 and the polyethyleneoxide content may comprise 20% to 80% by weight. Preferably, thesesurfactants are in liquid form and particularly satisfactory surfactantsare available as those marketed as Pluronics® L62 and Pluronics® L64.

Alkylmonoglyocosides and alkylpolyglycosides which find use in thepresent inventive compositions include known nonionic surfactants whichare alkaline and electrolyte stable. Alkylmonoglycosides andalkylpolyglycosides are prepared generally by reacting a monosaccharide,or a compound hydrolyzable to a monosaccharide with an alcohol such as afatty alcohol in an acid medium. Various glycoside and polyglycosidecompounds including alkoxylated glycosides and processes for making themare disclosed in U.S. Pat. Nos. 2,974,134; 3,219,656; 3,598,865;3,640,998; 3,707,535, 3,772,269; 3,839,318; 3,974,138; 4,223,129 and4,528,106 the contents of which are incorporated by reference.

One exemplary group of such useful alkylpolyglycosides include thoseaccording to the formula:R₂O—(C_(n)H_(2n)O)_(r)—(Z)_(x)wherein:

-   R₂ is a hydrophobic group selected from alkyl groups, alkylphenyl    groups, hydroxyalkylphenyl groups as well as mixtures thereof,    wherein the alkyl groups may be straight chained or branched, and    which contain from about 8 to about 18 carbon atoms, n has a value    of 2–8, especially a value of 2 or 3;-   r is an integer from 0 to 10, but is preferably 0,-   Z is derived from glucose; and,-   x is a value from about 1 to 8, preferably from about 1.5 to 5.    Preferably the alkylpolyglycosides are nonionic fatty    alkylpolyglucosides which contain a straight chain or branched chain    C₈–C₁₅ alkyl group, and have an average of from about 1 to 5 glucose    units per fatty alkylpolyglucoside molecule. More preferably, the    nonionic fatty alkylpolyglucosides which contain straight chain or    branched C₈–C₁₅ alkyl group, and have an average of from about 1 to    about 2 glucose units per fatty alkylpolyglucoside molecule.

A further exemplary group of alkyl glycoside surfactants suitable foruse in the practice of this invention may be presented by the followingformula (A):RO—(R₁O)_(y)—(G)_(x)—Z_(b)  (A)wherein:

-   R is a monovalent organic radical containing from about 6 to about    30, preferably from about 8 to 18 carbon atoms,-   R₁ is a divalent hydrocarbon radical containing from about 2 to    about 4 carbon atoms,-   y is a number which has an average value from about 0 to about 1 and    is preferably 0,-   G is a moiety derived from a reducing saccharide containing 5 or 6    carbon atoms; and,-   x is a number having an average value from about 1 to 5 (preferably    from 1.1 to 2);-   Z is O₂M¹,

O(CH₂), CO₂M¹, OSO₃M¹, or O(CH₂)SO₃M¹;

-   R₂ is (CH₂)CO₂M¹ or CH═CHCO₂M¹; (with the proviso that Z can be O₂M¹    only if Z is in place of a primary hydroxyl group in which the    primary hydroxyl-bearing carbon atom, —CH₂OH, is oxidized to form a

group)

-   b is a number of from 0 to 3x+1 preferably an average of from 0.5 to    2 per glycosal group;-   p is 1 to 10,-   M¹ is H⁺ or an organic or inorganic counterion, particularly cations    such as, for example, an alkali metal cation, ammonium cation,    monoethanolamine cation or calcium cation. As defined in Formula (A)    above, R is generally the residue of a fatty alcohol having from    about 8 to 30 and preferably 8 to 18 carbon atoms. Examples of such    alkylglycosides as described above include, for example APG 325 CS    Glycoside® which is described as being a 50% C₉–C₁₁ alkyl    polyglycoside, also commonly referred to as D-glucopyranoside,    (commercially available from Henkel KGaA) and Glucopon® 625 CS which    is described as being a 50% C₁₀–C₁₆ alkyl polyglycoside, also    commonly referred to as a D-glucopyranoside, (ex. Henkel).

Further nonionic surfactants which may be included in the inventivecompositions include alkoxylated alkanolamides, preferably C8–C24 alkyldi(C2–C3 alkanol amides), as represented by the following formula:R₅—CO—NH—R₆—OHwherein R₅ is a branched or straight chain C₈–C₂₄ alkyl radical,preferably a C₁₀–C₁₆ alkyl radical and more preferably a C₁₂–C₁₄ alkylradical, and R₆ is a C₁–C₄ alkyl radical, preferably an ethyl radical.

The inventive compositions may also include a nonionic amine oxideconstituent. Exemplary amine oxides include:

-   (A) Alkyl di (lower alkyl) amine oxides in which the alkyl group has    about 10–20, and preferably 12–16 carbon atoms, and can be straight    or branched chain, saturated or unsaturated. The lower alkyl groups    include between 1 and 7 carbon atoms. Examples include lauryl    dimethyl amine oxide, myristyl dimethyl amine oxide, and those in    which the alkyl group is a mixture of different amine oxide,    dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine    oxide, and myristyl/palmityl dimethyl amine oxide,-   (B) Alkyl di (hydroxy lower alkyl) amine oxides in which the alkyl    group has about 10–20, and preferably 12–16 carbon atoms, and can be    straight or branched chain, saturated or unsaturated. Examples are    bis(2-hydroxyethyl) cocoamine oxide, bis(2-hydroxyethyl) tallowamine    oxide; and bis(2-hydroxyethyl) stearylamine oxide;-   (C) Alkylamidopropyl di(lower alkyl) amine oxides in which the alkyl    group has about 10–20, and preferably 12–16 carbon atoms, and can be    straight or branched chain, saturated or unsaturated. Examples are    cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl    amine oxide; and-   (D) Alkylmorpholine oxides in which the alkyl group has about 10–20,    and preferably 12–16 carbon atoms, and can be straight or branched    chain, saturated or unsaturated.

Preferably the amine oxide constituent is an alkyl di (lower alkyl)amine oxide as denoted above and which may be represented by thefollowing structure:

wherein each:

-   R₁ is a straight chained C₁–C₄ alkyl group, preferably both R₁ are    methyl groups; and,-   R₂ is a straight chained C₈–C₁₈ alkyl group, preferably is    C₁₀–C₁₄alkyl group, most preferably is a C₁₂ alkyl group.

Each of the alkyl groups may be linear or branched, but most preferablyare linear. Most preferably the amine oxide constituent is lauryldimethyl amine oxide. Technical grade mixtures of two or more amineoxides may be used, wherein amine oxides of varying chains of the R₂group are present. Preferably, the amine oxides used in the presentinvention include R₂ groups which comprise at least 50% wt., preferablyat least 60% wt. of C₁₂ alkyl groups and at least 25% wt. of C₁₄ alkylgroups, with not more than 15% wt. of C₁₆, C₁₈ or higher alkyl groups asthe R₂ group.

Of course the nonionic surfactant constituent, when present, my comprisetwo or more nonionic surfactants. In certain preferred embodiments theinventive compositions comprise at least one nonionic surfactant. Whenpresent, any nonionic surfactants present in the compositions of thepresent invention are desirably included in an amount of from about0.01% wt. to about 20% wt., more preferably, is present in an amount offrom about 0.1–20% wt., and most preferably is present in an amount offrom about 1 to about 10% wt.

The compositions according to the invention may optionally furthercomprise an alkyl ethoxylated carboxylate surfactant. In particular, thealkyl ethoxylated carboxylate comprises compounds and mixtures ofcompounds which may be represented by the formula:R₁(OC₂H₄)_(n)—OCH₂COO31 M⁺wherein R₁ is a C₄–C₈ alkyl, n is from about 3 to about 20, and M ishydrogen, a solubilizing metal, preferably an alkali metal such assodium or potassium, or ammonium or lower alkanolammonium, such astriethanolammonium, monoethanolammoniuin, or diisopropanolammonium. Thelower alkanol of such alkanolammonium will normally be of 2 to 4 carbonatoms and is preferably ethanol. Preferably, R1 is a C₁₂–C₁₅ alkyl, n isfrom about 7 to about 13, and M is an alkali metal counterion.

Examples of alkyl ethoxylated carboxylates contemplated to be useful inthe present invention include, but are not necessarily limited to,sodium buteth-3 carboxylate, sodium hexeth-4 carboxylate, sodiumlaureth-5 carboxylate, sodium laureth-6 carboxylate, sodium laureth-8carboxylate, sodium laureth-11 carboxylate, sodiumlaureth-13carboxylate, sodium trideceth-3 carboxylate, sodiumtrideceth-6 carboxylate, sodium trideceth-7 carboxylate, sodiumtrideceth-19 carboxylate, sodium capryleth-4 carboxylate, sodiumcapryleth-6 carboxylate, sodium capryleth-9 carboxylate, sodiumcapryleth-13carboxylate, sodium ceteth-13carboxylate, sodium C₁₂₋₁₅pareth-6 carboxylate, sodium C₁₂₋₁₅ pareth-7 carboxylate, sodium C₁₄₋₁₅pareth-8 carboxylate, isosteareth-6 carboxylate as well as the acidform. Sodiumlaureth-8 carboxylate, sodium laureth-13carboxylate,pareth-25-7 carboxylic acid are preferred. A particularly preferredsodium laureth-13 carboxylate can be obtained from Clariant Corp. underthe trade name Sandopan® LS-24.

When present, any alkyl ethoxylated carboxylate surfactant present inthe compositions of the present invention are desirably included in anamount of from about 0.1 to about 20% by weight, more preferably ispresent in an amount of from about 0.1–20% wt., and most preferably ispresent in an amount of from about 1 to about 10% wt. By way ofnon-limiting example exemplary amphoteric surfactants include one ormore water-soluble betaine surfactants which may be represented by thegeneral formula:

wherein R₁ is an alkyl group containing from 8 to 18 carbon atoms, orthe amido radical which may be represented by the following generalformula:

wherein R is an alkyl group having from 8 to 18 carbon atoms, a is aninteger having a value of from 1 to 4 inclusive, and R₂ is a C₁–C₄alkylene group. Examples of such water-soluble betaine surfactantsinclude dodecyl dimethyl betaine, as well as cocoamidopropylbetaine.

When present, any amphoteric surfactants present in the compositions ofthe present invention are desirably included in an amount of from about0.1 to about 20% by weight, more preferably is present in an amount offrom about 0.1–20% wt., and most preferably is present in an amount offrom about 1 to about 10% wt.

Most desirably, the total amount of detersive surfactants present in theinventive compositions, inclusive of the necessary anionic surfactantsand any further optional surfactants does not exceed about 20% wt., morepreferably does not exceed about 15% wt.

Optionally, but in many cases desirably, the inventive compositionscomprise one or more organic solvents. By way of non-limiting exampleexemplary useful organic solvents which may be included in the inventivecompositions include those which are at least partially water-misciblesuch as alcohols (e.g., low molecular weight alcohols, such as, forexample, ethanol, propanol, isopropanol, and the like), glycols (suchas, for example, ethylene glycol, propylene glycol, hexylene glycol, andthe like), water-miscible ethers (e.g. diethylene glycol diethylether,diethylene glycol dimethylether, propylene glycol dimethylether),water-miscible glycol ether (e.g. propylene glycol monomethylether,propylene glycol mono ethylether, propylene glycol monopropylether,propylene glycol monobutylether, ethylene glycol monobutylether,dipropylene glycol monomethylether, diethyleneglycol monobutylether),lower esters of monoalkylethers of ethylene glycol or propylene glycol(e.g. propylene glycol monomethyl ether acetate), and mixtures thereof.Glycol ethers having the general structure R_(a)—R_(b)—OH, wherein R_(a)is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbonatoms, and R_(b) is an ether condensate of propylene glycol and/orethylene glycol having from one to ten glycol monomer units. Of course,mixtures of two or more organic solvents may be used in the organicsolvent constituent.

When present, the organic solvent constituent may be present in amountsof from about 0.1 to about 20% by weight, more preferably is present inan amount of from about 0.1–10% wt., and most preferably is present inan amount of from about 1 to about 10% wt.

According to certain particularly preferred embodiments, the inventivecompositions exclude added organic solvents, particularly thosedescribed immediately above. While it is recognized that organicsolvents may be present as carriers for certain other constituentsessential to the present invention, and these may be present; generallythe total amount of such organic solvents included in constituentsprovided from supplies, if present, is less than about than 0.1% wt.,more preferably less than 0.05% wt. and most preferably comprise noorganic solvents as described above. According to such certainparticularly preferred embodiments, the inventive compositions includeno organic solvents which are added other than those which may or maynot be present in one or more of the constituents from the supplierthereof. According to especially particularly preferred embodiments, theinventive compositions include no organic solvents.

While optional, the compositions of the invention may further include anoxidizing agent, which is preferably a peroxyhydrate or other agentwhich releases hydrogen peroxide in aqueous solution. Such materials areper se, known to the art. Such peroxyhydrates are to be understood as toencompass hydrogen peroxide as well as any material or compound which inan aqueous composition yields hydrogen peroxide. Examples of suchmaterials and compounds include without limitation: alkali metalperoxides including sodium peroxide and potassium peroxide, alkaliperborate monohydrates, alkali metal perborate tetrahydrates, alkalimetal persulfate, alkali metal percarbonates, alkali metalperoxyhydrate, alkali metal peroxydihydrates, and alkali metalcarbonates especially where such alkali metals are sodium or potassium.Further useful are various peroxydihydrate, and organic peroxyhydratessuch as urea peroxide. Desirably the oxidizing agent is hydrogenperoxide.

Desirably the oxidizing agent, especially the preferred hydrogenperoxide is present in the inventive compositions in an amount of fromabout 0.01% wt. to about 10.0% wt., based on the total weight ofthecomposition of which it forms a part.

Minor amounts of stabilizers such as one or more organic phosphonates,stannates, pyrophosphates, as well as citric acid as well as citric acidsalts may be included and are considered as part of the oxidizing agent.The inclusion of one or more such stabilizers aids in reducing thedecomposition of the hydrogen peroxide due to the presence of metal ionsand or adverse pH levels in the inventive compositions.

The compositions of the present invention can also optionally compriseone or more further constituents which are directed to improving theaesthetic or functional features of the inventive compositions. By wayof non-limiting example such further constituents include one or morecoloring agents, fragrances and fragrance solubilizers, viscositymodifying agents, other surfactants, pH adjusting agents and pH buffersincluding organic and inorganic salts, optical brighteners, opacifyingagents, hydrotropes, antifoaming agents, enzymes, anti-spotting agents,anti-oxidants, preservatives, and anti-corrosion agents. When one ormore of the optional constituents is added, i.e., fragrance and/orcoloring agents, the esthetic and consumer appeal of the product isoften favorably improved. The use and selection of these optionalconstituents is well known to those of ordinary skill in the art. Whenpresent, the one or more optional constituents present in the inventivecompositions do not exceed about 20% wt., preferably do not exceed 15%wt., and most preferably do not exceed 10% wt.

Certain optional constituents which are nonetheless desirably present inthe inventive compositions are pH adjusting agents and especially pHbuffers. Such pH buffers include many materials which are known to theart and which are conventionally used in hard surface cleaning and/orhard surface disinfecting compositions. By way of non-limiting examplepH adjusting agents include phosphorus containing compounds, monovalentand polyvalent salts such as of silicates, carbonates, and borates,certain acids and bases, tartrates and certain acetates. Furtherexemplary pH adjusting agents include mineral acids, basic compositions,and organic acids, which are typically required in only minor amounts.By way of further non-limiting example pH buffering compositions includethe alkali metal phosphates, polyphosphates, pyrophosphates,triphosphates, tetraphosphates, silicates, metasilicates, polysilicates,carbonates, hydroxides, and mixtures of the same. Certain salts, such asthe alkaline earth phosphates, carbonates, hydroxides, can also functionas buffers. It may also be suitable to use as buffers such materials asaluminosilicates (zeolites), borates, aluminates and certain organicmaterials such as gluconates, succinates, maleates, and their alkalimetal salts. When present, the pH adjusting agent, especially the pHbuffers are present in an amount effective in order to maintain the pHof the inventive composition within a target pH range.

As the compositions are largely aqueous in nature, and comprises as thebalance of the composition water in to order to provide to 100% byweight of the compositions of the invention. The water may be tap water,but is preferably distilled and is most preferably deionized water. Ifthe water is tap water, it is preferably substantially free of anyundesirable impurities such as organics or inorganics, especiallymineral salts which are present in hard water which may thus undesirablyinterfere with the operation of the constituents present in the aqueouscompositions according to the invention.

The inventive compositions provide certain technical benefits when usedon hard surfaces, particularly: satisfactory removal of hard waterstains, satisfactory removal of soap scum stains, and satisfactorydisinfection or sanitization of hard surfaces. In preferred embodiments,the compositions are readily pourable and are be desirably provided as aready to use pourable product in a manually squeezable (manuallydeformable) bottle. In use, the consumer generally applies an effectiveamount of the composition and within a few moments thereafter, wipes offthe treated area with a rag, towel, brush or sponge, usually adisposable paper towel or sponge. In certain applications, however,especially where undesirable stain deposits are heavy, the compositionaccording to the invention may be left on the stained area until it haseffectively loosened the stain deposits after which it may then be wipedoff, rinsed off, or otherwise removed. For particularly heavy depositsof such undesired stains, multiple applications may also be used.

A particularly advantageous feature of the inventive compositions isthat as the suspended inclusions are visibly discrete and visiblydiscernible to the consumer, these same inclusions are visible to theconsumer on hard surfaces to which the inventive compositions have beenapplied. This permits for ready visual inspection of the coverage of thehard surface by an inventive composition immediately after applicationof the composition by a consumer. Such provides not only an attractiveattribute to commercial products based on such compositions but alsoprovides a visual indicator to the consumer of thorough coverage andcontact with hard surfaces. This visual indicator provides an importantmeans whereby the consumer may visually inspect a surface, particularlya surface wherein the presence of undesired microorganisms is suspected,to ensure that thorough coverage and contact with said hard surface isrealized. As is known, physical contact between the inventivecomposition and undesired microorganisms is required in order to theinventive compositions to provide a disinfecting effect.

An important technical characteristic lies in rheology of the inventivecompositions. The compositions may be described as being rheopectic atlower shear rates, an especially upon standing in quiescent state, butare thixotropic at higher shear rates. Such dual properties are veryadvantageous, as when the compositions are at rest in a container, e.g.,upon standing, their rheopectic behavior provides for the stablesuspension of the inclusions described herein. When it is desired todispense the compositions from a container especially through the nozzleof a bottle, the thixotropic characteristics of the compositions permitfor their dispensing through the nozzle of such a bottle. Ideally, afterbeing dispensed from such a squeezable bottle onto a surface, especiallyan inclined surface the compositions return to a quiescent state andonce again display a rheopectic behavior. Furthermore, as at least someof the suspended inclusions are delivered from the composition and ontothe surface, these inclusions are present on the surface and provide auseful indicator as to the coverage of the dispensed composition ontothe surface. Preferably the inventive compositions are provided in anon-pressurized squeeze bottle package which provides for the dispensingof the compositions through a nozzle, but not through a trigger spray,other pump mechanism or via an aerosol nozzle.

The inventive compositions are desirably provided as a ready to useproduct which may be directly applied to a hard surface. By way ofexample, hard surfaces suitable for coating with the polymer includesurfaces composed of refractory materials such as: glazed and unglazedtile, brick, porcelain, ceramics as well as stone including marble,granite, and other stones surfaces; glass; metals; plastics e.g.polyester, vinyl; fiberglass, Formica®, Corian® and other hard surfacesknown to the industry. Hard surfaces which are to be particularlydenoted are lavatory fixtures such as shower stalls, bathtubs andbathing appliances (racks, curtains, shower doors, shower bars) toilets,bidets, wall and flooring surfaces especially those which includerefractory materials and the like. Further hard surfaces which are to bedenoted are those associated with kitchen environments and otherenvironments associated with food preparation, including cabinets andcountertop surfaces as well as walls and floor surfaces especially thosewhich include refractory materials, plastics, Formica®, Corian® andstone. Still further hard surfaces include those associated with medicalfacilities, e.g., hospitals, clinics as well as laboratories, e.g.,medical testing laboratories.

The compositions according to the invention are easily produced by anyof a number of known art techniques. Conveniently, a part of the wateris supplied to a suitable mixing vessel further provided with a stirreror agitator, and while stirring, the remaining constituents are added tothe mixing vessel, including any final amount of water needed to provideto 100% wt. of the inventive composition.

The following examples below illustrate exemplary formulations andpreferred formulations of the inventive composition. It is to beunderstood that these examples are presented by means of illustrationonly and that further useful formulations fall within the scope of thisinvention and the claims may be readily produced by one skilled in theart and not deviate from the scope and spirit of the invention.Throughout this specification and in the accompanying claims, weightpercents of any constituent are to be understood as the weight percentof the active portion of the referenced constituent, unless otherwiseindicated.

EXAMPLES

Exemplary formulations illustrating certain preferred embodiments of theinventive compositions and described in more detail in Table 1 belowwere formulated generally in accordance with the following protocol.

Into a suitably sized vessel, a measured amount of water was providedafter which the constituents were added in the following sequence:thickening agents, surfactant(s), acid and then the remainingconstituents. Mixing, which generally lasted from 5 minutes to 120minutes was maintained until the particular formulation appeared to behomogeneous. The exemplary compositions were readily pourable, andretained well mixed characteristics (i.e., stable mixtures) uponstanding. The constituents may be added in any order.

Examples of inventive formulations are shown in Table 1 below (theindicated constituents are provided as “100% active”) wherein theamounts of each named constituents are indicated in % w/w. Deionizedwater was added in “quantum sufficient” to provide the balance to 100parts by weight of the compositions.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex.11 Ex. 12 hydroxyethylcellulose 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 — xanthan gum 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.2 gellangum — — — — — — — — — — — 0.05 sodium lauryl sulfate 2.0 2.0 2.0 2.0 2.02.0 2.0 2.0 2.0 2.0 2.0 2.0 citric acid 4.0 2.0 2.0 2.0 2.0 2.0 2.0 2.02.0 2.0 2.0 2.0 formic acid — 2.0 — — — — — — — — — — malonic acid — — —— 2.0 — — — — — — — maleic acid — — — — — 2.0 — — — — — — adipic acid —— 2.0 — — — — — — — — — boric acid — — — 2.0 — — — — — — — — lactic acid— — — — — — — — — 2.3 — 2.0 glycolic acid — — — — — — — — — — 2.0 —malic acid — — — — — — 2.0 — — — — — acetic acid — — — — — — — 2.0 — — —— sorbic acid — — — — — — — — 2.0 — — — sodium hydroxide 0.5 0.77 0.340.34 0.34 0.34 0.34 0.34 0.34 0.28 0.34 0.34 dye 1 1 1 1 1 1 1 1 1 1 1 —fragrance 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.21alginate beads 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.3 pH 2.922.92 2.99 2.94 3.01 3.01 3.0 2.95 2.98 2.88 2.96 — di water q.s. q.s.q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.The identity of the individual constituents indicated above is listed onthe following table wherein is indicated the generic name, thecommercial preparation used, the percent active weight (% w/w basis) ofthe compound identified by the generic name, and in some cases thesupplier of the commercial preparation:

TABLE 2 hydroxyethylcellulose CELLOSIZE QP-100MH (100%) (ex. UnionCarbide, division of Dow Chemical) xanthan gum KELZAN ASXT (100%) (ex.Kelco) gellan gum KELCOGEL AFT (100%) (ex. Kelco) sodium lauryl sulfateStepanol WAC (30%) (ex. Stepan Co.), except for Ex. 12 where StepanolLCP (30%) a low cloud point sodium lauryl sulfate was used citric acidanhydrous citric acid (100%) (ex. ADM) formic acid formic acid (94%)malonic acid malonic acid (99%) maleic acid maleic acid (100%) adipicacid adipic acid (98%) boric acid boric acid (99.5%) lactic acid lacticacid (88%) glycolic acid glycolic acid (70%) (ex. DuPont) malic acidmalic acid (100%) acetic acid acetic acid (100%) sorbic acid sorbic acid(100%) sodium hydroxide NaOH pellets, anhydrous (100%) dye 1% aqueoussolution of a FD&C yellow dye fragrance proprietary composition alginatebeads alginate based particulate material compsiring less than 5% wt ofcalcium alginate, less than 0.01% wt. of a pigment, less than 5% wt. ofTiO₂ and the balance to 100% wt. water drained from an aqueous carriercontaining 2% calcium chloride in solution (ex. geniaLabsBiotechnologie, Germany) di water deionized waterCertain of the compositions described on Table 1 above were tested toevaluate certain technical characteristics of the compositions.Evaluation of Composition Stability:

Certain of the compositions described on Table 1 were evaluated toobserve the stability of the alginate beads in the compositionsfollowing storage of the compositions under accelerated ageing testing,wherein the compositions were stored for 1 week at 49° C. The resultsare indicated in the following Table:

TABLE 3 Ex. 1 stable Ex. 2 stable Ex. 3 swell Ex. 4 swell Ex. 5 swellEx. 6 swell Ex. 7 stable Ex. 8 swell Ex. 9 swell Ex. 10 stable Ex. 11stable

A result of “stable” indicated that the suspended inclusions based onthe alginate based particulate materials did not change in from theirinitial appearance at the conclusion of the test. A result of “swell”indicated that the suspended inclusions based on the alginate basedparticulate materials slightly to somewhat changed in from their initialappearance at the conclusion of the test. In all of the formulationshowever the alginate based particulate materials were stably suspendedinclusions.

All of the compositions of Table 1, after being manually shaken and thenallowed to return to a quiescent state by permitting them to stand on alaboratory bench tabletop at room temperature (approx. 20° C.) for 48hours, exhibited the behavior that the majority of (at least 95% of) thealginate beads do not drop more than 5%, often not more than 2% of theiroriginal distance as measured from the bottom of the container in whichthe particular inventive composition was present for a period of atleast 4 weeks when maintained in a quiescent state at room temperature.

Evaluation of Viscosity:

The viscosity of the compositions were evaluated utilizing using anLVT-II Brookfield Viscometer, #2 spindle at 20 rpm and 20° C. Theviscosity of all of the compositions according to Examples 1–11 was inthe range of 1100–1500 cps. The viscosity of the composition accordingto Ex. 12 measured as noted above was 306 cps.

Evaluation of Efficacy against Hard Water Stains:

A formulation according to the invention, namely the formulationdescribed as “Ex. 10” on Table 1 was evaluated for its efficacy inremoving hard water stains. Such hard water stains are also referred toas “limescale”. The test protocol was as follows:

Five sample marble tiles, each measuring 5.75 inches by 2.88 inches by0.37 inches were washed and dried for one hour in a laboratory oven at80° C. The tiles were then weighed, and thereafter immersed in 900 ml.of the formulation according to Ex. 10 for 10 seconds, removed from theformulation and thereafter allowed to rest at room temperature (approx.20° C.) on a laboratory bench. Thereafter the tiles were thoroughlyrinsed with deionized water, manually dried using a laboratory wipe(Kimwipe®), and then again dried for one hour at 80° C. in a laboratoryoven. Thereafter the tiles were removed, and allowed to cool to roomtemperature and reweighed. The results of this test, including averageresults for limescale removal and % weight loss are indicated in thefollowing table.

TABLE 4 sample limescale % wt. loss of tile # initial weight (g) finalweight (g) removed (g) sample tile 1 294.0960 294.0490 0.0470 0.0160 2293.4320 293.3760 0.0560 0.0191 3 295.4210 295.3680 0.0530 0.0179 4298.8390 298.7870 0.0520 0.0174 5 304.0830 304.0290 0.0540 0.0178 0.05240.0176 (avg.) (avg.)

The results indicate the loss of carbonates (calcium carbonate,magnesium carbonates, etc.) from the marble compositions of the tiles,and demonstrate the efficacy of the inventive composition in the removalof inorganic carbonates, a major constituent in limescale.

As a comparative example, the same test protocol as indicated above wasrepeated but using a commercially available bathroom cleaning product,“Lysol® Cling Toilet Bowl Cleaner—Country Scent” instead of theformulation according to Ex. 10. The results of this test are indicatedin the following table.

TABLE 4 (comparative example) sample limescale % wt. loss of tile #initial weight (g) final weight (g) removed (g) sample tile 6 295.8070295.7960 0.0110 0.0037 7 296.8830 296.8690 0.0140 0.0047 8 291.8520291.8400 0.0120 0.0041 9 300.3410 300.3370 0.0040 0.0013 10 299.4050299.3920 0.0130 0.0043 0.0108 0.0036 (avg.) (avg.)

As can be seen by comparing the results of the foregoing tables, thesample tiles treated with the inventive composition exhibited goodefficacy at removal of inorganic carbonates from the sample tiles, whilethe tiles treated with the prior art composition demonstrated much lowerefficacy at removal of inorganic carbonates.

Evaluation of Antimicrobial Efficacy:

Several of the exemplary formulations described in more detail on Table1 above were evaluated in order to evaluate their antimicrobial efficacyagainst Staphylococcus aurelis (gram positive type pathogenic bacteria)(ATCC 6538), Salmonella choleraesuis (gram negative type pathogenicbacteria) (ATCC 10708), Escheria coli (gram negative type pathogenicbacteria) (ATCC 11229) and Pseudomonas aeruginosa (ATCC 15442). Thetesting was performed generally in accordance with the protocolsoutlined in “Use-Dilution Method”, Protocols 955.14, 955.15 and 964.02described in Chapter 6 of “Official Methods of Analysis”, 16^(th)Edition, of the Association of Official Analytical Chemists; “Germicidaland Detergent Sanitizing Action of Disinfectants”, 960.09 described inChapter 6 of “Official Methods of Analysis”, 15^(th) Edition, of theAssociation of Official Analytical Chemists; or American Society forTesting and Materials (ASTM) E 1054-91 the contents of which are hereinincorporated by reference. This test is also commonly referred to as the“AOAC Use-Dilution Test Method”. Testing was performed on the inventiveformulation described as “Ex. 10” described on Table 1, above atdilutions of 1 part formulation to 25 parts water.

As is appreciated by the skilled practitioner in the art, the results ofthe AOAC Use-Dilution Test Method indicates the number of testsubstrates wherein the tested organism remains viable after contact for10 minutes with at test disinfecting composition/total number of testedsubstrates (cylinders) evaluated in accordance with the AOACUse-Dilution Test. Thus, a result of “0/60” indicates that of 60 testsubstrates bearing the test organism and contacted for 10 minutes in atest disinfecting composition, 0 test substrates had viable (live) testorganisms at the conclusion of the test. Such a result is excellent,illustrating the excellent disinfecting efficacy of the testedcomposition.

Results of the antimicrobial testing are indicated on the Table, below.The reported results indicate the number of test cylinders with livetest organisms/number of test cylinders tested for each exampleformulation and organism tested.

TABLE 5 Test Results Conclusion Staphylococcus aureus 1/60 PassSalmonella choleraesuis 1/60 Pass Escheria coli 1/60 Pass Pseudomonasaeruginosa 1/60 Pass

As may be seen from the results indicated above, the compositionsaccording to the invention provide excellent cleaning benefits to hardsurfaces, including hard surfaces with difficult to remove stains. Theseadvantages are further supplemented by the excellent antimicrobialefficacy of these compositions against known bacteria commonly found inbathroom, kitchen and other environments. Such advantages clearlyillustrate the superior characteristics of the compositions, thecleaning and antimicrobial benefits attending its use which is notbefore known to the art.

1. A hard surface cleaning and/or disinfecting composition whichcomprises: a water soluble organic acid constituent; at least oneanionic surfactant; suspended inclusions which appear as visiblydiscernible, discrete particulate materials and wherein said inclusionsare based on alginate beads; a thickener consisting essentially of aconstituent; optionally, at least one further detersive surfactantselected from nonionic, amphoteric and zwitterionic surfactants;optionally, at least one organic solvent; optionally, one or moreconstituents for improving the aesthetic or functional features of theinventive compositions; and water; wherein the composition has a pH of 5or less.
 2. The composition according to claim 1 wherein the acidconstituent contains an acid selected from the group consisting of:citric acid, sorbic acid, acetic acid, formic acid, maleic acid, adipicacid, lactic acid, malic acid, malonic acid, glycolic acid, and mixturesthereof.
 3. The composition according to claim 2 wherein the acidconstituent comprises citric acid.
 4. The composition according to claim1 wherein the composition comprises an organic solvent.
 5. Thecomposition according to claim 4 wherein the organic solvent is selectedfrom alcohols, glycols, water miscible ethers, water miscible glycolethers, monalkylether esters, and mixtures thereof.
 6. The compositionaccording to claim 5 wherein the organic solvent is selected fromalcohols, water miscible glycol ethers and mixtures thereof.
 7. Thecomposition according to claim 5 wherein the organic solvent is analcohol.
 8. The composition according to claim 1 wherein thecompositions exclude added organic solvents.
 9. The compositionaccording to claim 1 wherein the majority of the inclusions do not dropmore than 7% of their original distance as measured from the bottom ofthe container in which the inventive composition is present when theyhave returned to a quiescent state following manual shaking.
 10. Thecomposition according to claim 9 wherein the majority of the inclusionsdo not drop more than 7% of their original distance as measured from thebottom of the container in which the inventive composition is presentwhen they have returned to a quiescent state following manual shakingwhen measured after 72 hours when left in a quiescent state at roomtemperature.
 11. The composition according to claim 10 wherein themajority of the inclusions do not drop more than 7% of their originaldistance as measured from the bottom of the container in which theinventive composition is present when they have returned to a quiescentstate following manual shaking when measured after 5 days when left in aquiescent state at room temperature.
 12. The composition according toclaim 11 wherein the majority of the inclusions do not drop more than 7%of their original distance as measured from the bottom of the containerin which the inventive composition is present when they have returned toa quiescent state following manual shaking when measured after 10 dayswhen left in a quiescent state at room temperature.
 13. The compositionaccording to claim 12 wherein the majority of the inclusions do not dropmore than 7% of their original distance as measured from the bottom ofthe container in which the inventive composition is present when theyhave returned to a quiescent state following manual shaking whenmeasured after 14 days when left in a quiescent state at roomtemperature.
 14. The composition according to claim 1 wherein the pH isfrom about 1 to about
 5. 15. The composition according to claim 14wherein the pH is from about 1 to about
 4. 16. The composition accordingto claim 15 wherein the pH is from about 1 to about
 3. 17. Thecomposition according to claim 1 having a viscosity of from about 750 toabout 1500 centipoise, as measured at room temperature on a RVTBrookfield viscometer, spindle #2, at 60 rpm.
 18. A hard surfacecleaning and/or disinfecting composition according to claim 1 whereinsaid composition exhibits antimicrobial efficacy against at least one ofthe following organisms: Staphylococcus aureus (gram positive typepathogenic bacteria) (ATCC 6538), Salmonella choleraesuis (gram negativetype pathogenic bacteria) (ATCC 10708), Escheria coli (gram negativetype pathogenic bacteria) (ATCC 11229) and Pseudomonas aeruginosa (ATCC15442) of not more than 1/60 according to the AOAC Use-Dilution TestMethod.
 19. A method of treating a hard surface comprising applying aneffective amount of a composition according to claim 1 to a surface inneed of treatment.
 20. A hard surface cleaning and/or disinfectingcomposition according to claim 1 wherein: the thickener constituentconsists essentially of one or more cellulose derivatives selected fromethyl cellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose,carboxy methyl cellulose, carboxy methyl hydroxyethyl cellulose,hydroxypropyl cellulose, hydroxy propyl methyl cellulose, and ethylhydroxy ethyl cellulose.
 21. A hard surface cleaning and/or disinfectingcomposition according to claim 1 wherein the thickener constituentcomprises xanthan gum or gellan gum.